4-methoxy-1-hexene | 147283-01-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methoxy-1-hexene
• 英文别名: 4-Methoxyhex-1-ene
• CAS: 147283-01-0
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: MXKALERJRLLYOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis[1,1-di(trifluoromethyl)ethoxy][(2,6-diisopropylphenyl)imino](2-methyl-2-phenylpropylidene)molybdenum 、 4-methoxy-1-hexene 以 正戊烷 为溶剂， 以66%的产率得到
  参考文献：
  名称：

  Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents

  摘要：

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.

  DOI：

  10.1021/om00027a028
• 作为产物：
  描述：

  3-methoxy-5-hexen-1-ol 在 叔丁基锂 、 三乙胺 、 sodium iodide 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 、 正戊烷 为溶剂， 反应 1.83h， 生成 4-methoxy-1-hexene
  参考文献：
  名称：

  烷氧基取代的5-己烯基锂环化的立体化学：溶剂和碘化锂对非对映选择性的影响

  摘要：

  4-甲氧基-5-己烯基锂，4-（甲氧基甲氧基）-5-己烯基锂，4-叔丁氧基-5-己烯基锂和3-甲氧基-5-己烯基锂环化的立体化学通过低温锂-碘交换得到相应的碘化物，已在多种溶剂系统中进行了研究。这些研究的结果表明，烷氧基取代的5-己烯基锂环化的立体化学结果可能会受到进行闭环的介质的深刻影响。这些通常具有显着溶剂作用的病因归因于某些亲硫性配体竞争性络合碘化锂盐的能力，碘化锂盐是作为用于制备有机锂的交换反应的副产物而存在的。

  DOI：

  10.1016/j.tet.2005.01.042

文献信息

• [EN] USE OF 3-PHENYLURACIL DERIVATIVES FOR THE DESICCATION AND ABSCISSION OF PLANT PARTS
  申请人：BASF AKTIENGESELLSCHAFT

  公开号：WO1993011669A1

  公开（公告）日：1993-06-24

  (DE) Verwendung von 3-Phenylurazil-Derivaten (I) mit R1 = H, Alkyl, Halogenalkyl, Formyl, Alkanoyl, Alkenyl oder Alkinyl; R2 = über -O-, -O-CO-, -O-CS- oder -O-SO2- gebundene Gruppe, -CO-NR7R8 oder -CO-R9 (R7-R9 vgl. Beschreibung); R3 = Halogen oder CN; R4 = H oder Halogen; R5 = H, Halogen oder Alkyl; R6 = Alkyl oder Halogenalkyl; oder R5+R6 = Tri- oder Tetramethylen, sowie die Enolether derjenigen Verbindungen (I), in denen R1 C1-C4-Alkyl, C2-C5-Alkenyl oder C3-C5-Alkinyl bedeutet, es sei denn, R2 = über -O-SO2- gebundene Gruppe oder -CO-O-CH2-CH2-ON=C(R12,R13) mit R12 und R13 = C1-C4-Alkyl, sowie die landwirtschaftlich brauchbaren Salze und Enolether derjenigen Verbindungen der Formel (I), in denen R1 = Wasserstoff, zur Desikkation und Abszission von Pflanzenorganen.(EN) The invention concerns the use, for the desiccation and abscission of plant organs, of 3-phenyluracil derivatives of the formula (I), in which R1 = H, alkyl, haloalkyl, formyl, alkanoyl, alkenyl or alkinyl; R2 = -CO-NR7R8 or -CO-R9 (in which R7 to R9 are as defined in the description) or a group bound by -O-, -O-CO-, -O-CS- or -O-SO2-; R3 = halogen or CN; R4 = H or halogen; R5 = H, halogen or alkyl and R6 = alkyl or haloalkyl or R5 + R6 = tri- or tetramethylene; as well as the enol ethers of such compounds of formula (I) in which R1 is C1-C4 alkyl, C2-C5 alkenyl or C3-C5 alkinyl provided that R2 = -CO-O-CH2-CH2-ON=C(R12,R13) (in which R12 and R13 = C1-C4 alkyl) or a group bound by -O-SO2-, as well as the agriculturally useful salts and enol ethers of such compounds of formula (I) in which R1 = hydrogen.(FR) Utilisation de dérivés de 3-phénylurazile de formule (I) dans laquelle R1 = H, alkyle, halogéno-alkyle, formyle, alcanoyle, alcényle ou alkinyle; R2 = groupe lié par l'intermédiaire de -O-, -O-CO-, -O-CS- ou -O-SO2-, -CO-NR7R8 ou -CO-R9 (R7-R9: voir description); R3 = halogène ou CN; R4 = H ou halogène; R5 = H, halogène ou alkyle; R6 = alkyle ou halogèno-alkyle; ou R5 + R6 = tri- ou tétraméthylène, ainsi que les éthers énoliques des composés(I), dans lesquels R1 désigne un alkyle en C1-C4, un alcényle en C2-C5 ou un alkinyle en C3-C5, à condition que R2 = groupe lié par l'intermédiaire de -O-SO2- ou -CO-O-CH2-ON=C(R12,R13) où R12 et R13 = alkyle en C1-C4, ainsi que les sels et éthers énoliques, utilisables en agriculture, des composés de formule (I), dans lesquels R1 = hydrogène, pour la dessiccation et l'éxcision d'organes végétaux.

  Die Verwendung von 3-Phenyluracil-Derivaten (I) mit R1 = H, Alkyl, Haloalkyl, Formyl, Alkanoyl, Alkenyl oder Alkinyl; R2 = über -O-, -O-CO-, -O-CS- ou -O-SO2- gebundene Gruppe, -CO-NR7R8 ou -CO-R9 (wobei R7 bis R9 wie im Beschreibung genannt werden); R3 =卤素 oder CN; R4 = H oder卤素; R5 = H,卤素 oder Alkyl und R6 = Alkyl oder Haloalkyl oder R5+R6 = tri- oder Tetramethylen; sowie die Enolether der Martinezungen (I), in denen R1 ein C1-C4-Alkyl, C2-C5-Alkenyl oder C3-C5-Alkinyl ist, falls R2 = über -O-SO2- gebundene Gruppe oder -CO-O-CH2-CH2-ON=C(R12,R13) mit R12 und R13 = C1-C4-Alkyl, sowie die landwirtschaftlich brauchbaren Salze und Enolether der Martinezungen der Formel (I), in denen R1 = Wasserstoff, zur Desikkation und Entzinnung von Pflanzenorganien.
• US4867784A
  申请人：——

  公开号：US4867784A

  公开（公告）日：1989-09-19
• Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents
  作者：Harold H. Fox、Jin Kyu Lee、Lee Y. Park、Richard R. Schrock

  DOI：10.1021/om00027a028

  日期：1993.3

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.
• Stereochemistry of the cyclization of alkoxy-substituted 5-hexenyllithiums: effect of solvent and lithium iodide on diastereoselectivity
  作者：William F. Bailey、Xinglong Jiang

  DOI：10.1016/j.tet.2005.01.042

  日期：2005.3

  The stereochemistry of the cyclization of 4-methoxy-5-hexenyllithium, 4-(methoxymethoxy)-5-hexenyllithium, 4-tert-butoxy-5-hexenyllithium, and 3-methoxy-5-hexenyllithium, each of which was generated from the corresponding iodide by low-temperature lithium–iodine exchange, has been studied in a variety of solvent systems. The results of these studies demonstrate that the stereochemical outcome of the

  4-甲氧基-5-己烯基锂，4-（甲氧基甲氧基）-5-己烯基锂，4-叔丁氧基-5-己烯基锂和3-甲氧基-5-己烯基锂环化的立体化学通过低温锂-碘交换得到相应的碘化物，已在多种溶剂系统中进行了研究。这些研究的结果表明，烷氧基取代的5-己烯基锂环化的立体化学结果可能会受到进行闭环的介质的深刻影响。这些通常具有显着溶剂作用的病因归因于某些亲硫性配体竞争性络合碘化锂盐的能力，碘化锂盐是作为用于制备有机锂的交换反应的副产物而存在的。